Phosphoramidate ester insecticidal compositions

ABSTRACT

THIS INVENTION DISCLOSES THE INSECTICIAL USE OF COMPOUNDS OF THE FORMULA   (R1-(X3)M-P(=X1)(-Y)-X2-CH2-CO-N(-R2)-),(Z)N-PYRIDINE   WHEREIN R1 IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL AND   ((A)Q-PHENYL)-(CH2)P-   WHEREIN B IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL, ALKOXY, ALKYLTHIO, HALOGEN, NITRO, DIALKYLAMINO, ALKYLSULFOXIDE AND ALKYLSULFONE, R IS AN INTEGER FROM 0 TO 5, Q IS SELECTED FROM THE GROUP CONSISTING OF OXYGEN, SULFUR, ALKYLENE, ALKYLENEOXY AND ALKYLENETHIO, AND T IS AN INTEGER FRPM 0 TO 1; R2 IS ALKYL; Z IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL, ALKOXY, ALKYLTHIO, HALOGEN AND NITRO; AND N IS AN INTEGER FROM 0 TO 4.   ((B)R-PHENYL)-(Q)T-   WHEREIN A IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL, ALKOXY, ALKYLTHIO, HALOGEN, NITRO, DIALKYLAMINO, ALKYLSULFOXIDE AND ALKYLSULFONE, Q IS AN INTEGER FROM 0 TO 5, AND P IS AN INTEGER FROM 0 TO 3; X1 AND X2 AND X3 ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF OXYGEN AND SULFUR; M IS AN INTEGER FROM 0 TO 1; Y IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL, ALKOXY, ALKYLTHIO, AMINO, ALKYLAMINO, DIALKYLAMINO AND

United States Patent 3,816,620 PHOSPHORAMIDATE ESTER INSECTICIDALCOMPOSITIONS Sidney B. Richter, Chicago, and Leonard J. Stach,Riverside, lll., assignors to Velsicol Chemical Corporation,

Chicago, II].

No Drawing. Original application Nov. 25, 1968, Ser. No. 778,768, nowPatent No. 3,632,814. Divided and this application Feb. 12, 1971, Ser.No. 115,079

U.S. Cl. 424-200 4 Claims ABSTRACT OF THE DISCLOSURE This inventiondiscloses the insecticidal use of compounds of the formula H O R X=.,,--1 --X -cH,i JN N U-n) wherein R is selected from the groupconsisting of alkyl, alkenyl and wherein A is selected from the groupconsisting of alkyl, aklenyl, alkoxy, alkylthio, halogen, nitro,dialkylamino, alkylsulfo'xide and alkylsulfone, q is an integer from 0to 5, and p is an integer from 0 to 3; X X and X are independentlyselected from the group consisting of oxygen and sulfur; in is aninteger from O to 1; Y is selected from the group consisting of alkyl,alkenyl, alkoxy, alkylthio, amino, alkylamino, dialkylamino and Thisapplication is a divisional of our co-pending application Ser. No.778,768, filed Nov. 25, 1968, now U.S. Pat. No. 3,632,814 issued Jan. 4,1972.

This invention relates to new chemical compositions and moreparticularly relates to new compounds of the formula 3,816,620 PatentedJune 11, 1974 wherein R is selected from the group consisting of alkyl,alkenyl and wherein A is selected from the group consisting of alkyl,alkenyl, alkoxy, alkylthio, halogen, nitro, dialkylamino, alkylsulfoxideand alkylsulfone, q is an integer from O to 5, and p is an integer from0 to 3; X X and X are independently selected from the group consistingof oxygen and sulfur; m is an integer from 0 to 1; Y is selected fromthe group consisting of alkyl, alkenyl, alkoxy, alkylthio, amino,alkylamino, dialkylamino and wherein B is selected from the groupconsisting of alkyl, alkenyl, alkoxy, alkylthio, halogen, nitro,dialkylamino, alkylsulfoxide and alkylsulfone, r is an integer from 0 to5, Q is selected from the group consisting of oxygen, sulfur, alkylene,alkyleneoxy and alkylenethio, and tis an integer from O to 1; R isalkyl; Z is selected from the group consisting of alkyl, alkenyl,alkoxy, alkylthio, halogen and nitro; and n is an integer from 0 to 4.

In a preferred embodiment of this invention R is selected from the groupconsisting of lower alkyl, lower alkenyl and wherein A is selected fromthe group consisting of lower alkyl, lower alkenyl, lower alkoxy, loweralkylthio, ch1o rine, bromine, nitro and di(lower alkyl)amino, q is aninteger from 0 to 3, and p is an integer from 0 to 2; X X and X areindependently selected from the group consisting of oxygen and sulfur; mis an integer from 0 to 1; Y is selected from the group Consisting oflower alkyl, lower alkenyl, lower alkoxy, lower alkylthio, amino, loweralkylamino, di(lower alkyl)amino and wherein B is selected from thegroup consisting of lower alkyl, lower alkenyl, lower alkoxy, loweralkylthio, chlorine, bromine, nitro and di(lower alkyl)amino, r is aninteger from 0 to 3, Q is selected from the group consisting of oxygen,sulfur, alkylene of up to 4 carbon atoms, methyloxy, ethyloxy,methylthio and ethylthio, and t is an integer from 0 to 1; R is loweralkyl; Z is selected from the group consisting of lower alkyl, loweralkenyl, lower alkoxy, lower alkylthio, chlorine, bromine and nitro; andn is an integer from 0 to 3.

The new compounds of the present invention are un expectedly useful aspesticides particularly as insecticides and acaricides.

The compounds of the present invention can be readily prepared byreacting an alkali metal salt of a phosphorus acid of the formulawherein M is an alkali metal such as potassium; and X X X Y, R and m areas heretofore described, with an N-pyridyl-a-chloroacetamide of theformula CICHzPJ-N 0-11) (III) wherein R Z and n are as heretoforedescribed. This reaction can be effected by heating the above reactantsin an inert organic reaction medium at the reflux temperature of thereaction mixture for a period of from about 1 to about 48 hours. Thedesired product can then be recovered by first filtering the reactionmixture to remove the alkali metal chloride which is formed andthereafter stripping the mixture of the solvent used as the reactionmedium to yield the product as a residue. This residue can be used assuch to prepare valuable insecticidal and acaricidal compositions or itcan be further purified, if desired, by washing, extraction,recrystallizing, chromatography or other techniques well known in theart.

The phosphorus acid salts of Formula II, when not readily available, canbe prepared from their correspond ing acids by the methods described byMalatesta and Pizzotti, Chimica e Industria (Milan) 27, 6-10 (1945), andMelnikov and Grapov, Zhur. Vsesoyuz Khim. Obshchestva in D. I.Mendeleeva, 6, No. 1; 119-120 (1961).

The N-pyridyl-u-chloroacetamides of Formula III can be prepared byreacting chloroacetyl chloride with an aminopyridine oralkylaminopyridine having the desired substituents on the pyridine ring.This reaction can be effected by adding chloroacetyl chloride or asolution of chloroacetyl chloride in a suitable solvent such as ether,for example, to a solution of the aminopyridine or alkylaminopyridine inan inert organic solvent at a temperature below about 50 C. andpreferably at a temperature of from about 20 to about 30 C. in thepresence of an acid acceptor such as a tertiary amine or alkali metalhydroxide or carbonate. The desired product can then be recovered as theresidue upon evaporation of the solvents used, or by filtration of thereaction mixture if the product forms as a precipitate. The product canthen be used as such or can be further purified by conventionaltechniques for use in preparing the compounds of the present invention.

The manner in which the compounds of this invention can be preparedreadily is more specifically illustrated by the following examples.

EXAMPLE 1 Preparation of N-(6-methoxy-3-pyridyl)- a-chloroacetamide Asolution of 3-amino-6-methoxypyridine (25.0 grams) in absolute ether(160 ml.) was charged into a glass reaction flask equipped with amechanical stirrer, dropping funnel and thermometer. The solution wascooled to a temperature of about 0 C. and pyridine (18.1 ml.) was addedthereto. A solution of chloroacetyl chloride (17.0 ml.) in ether (40ml.) was then slowly added to the flask with stirring over a period ofabout 15 minutes resulting in the formation of a precipitate. Thetemperature of the reaction mixture was kept between about 0 to C.during the addition of the chloroacetyl chloride. After completion ofthe addition stirring was continued for a period of about 30 minutes.The solid precipitate which .4 had formed was then recovered byfiltration and was washed with aqueous sodium bicarbonate and then withwater. The washed product was then dried to yield the desired productN-(16-methoxy-3-pyridyl)-a-chloroacetamide as a white solid having amelting point of 117 to 118 C.

EXAMPLE 2 Preparation of S-[2-(6-methoxy-3-pyridylamino)2-ketoethyl]O-ethyl N-isopropylthiolophosphoramidate N-(6-methoxy 3pyridyl)-a-chloroacetamide (10.0 grams), acetone (175 ml.) and potassiumO-ethyl N-isopropylthiolophosphoramidate (16.5 grams) were charged intoa glass reaction flask equipped with a mechanical stirrer, thethermometer and reflux condenser. The reaction mixture was heated atreflux with stirring for a period of about 24 hours. After this time thereaction mixture was stripped of acetone on a steam bath leaving a redcolored residue. The residue was dissolved in ether (130 ml.) and waswashed with water. The washed solution was dried over sodium sulfate,was filtered and evaporated to yield a red oil. The oil was placed intoa vacuum desiccator and dried under vacuum (2.0 mm.) at room temperaturefor a period of about 4 hours. The oil was then allowed to stand forseveral days upon which it solidified to yield the desired productS-[2-(6-methoxy- 3-pyridylamino)2-ketoethyl] O-ethylN-isopropylthiolophosphoramidate as a crystalline solid having a meltingpoint of to 86 C.

EXAMPLE 3 Preparation of S-[2-(6-methoxy-3-pyridylamino)2-ketoethyl]O-ethyl N-2'-butylthiolophosphoramidate N-(6-methoxy-3-pyridyl) achloroacetamide (4.5 grams), acetone (150 ml.) and potassium 0-ethylN-tbutylthiolophosphoramidate (6.78 grams) were charged into a glassreaction vessel equipped with stirrer, thermometer and reflux condenser.The reaction mixture was heated at reflux, with stirring, for a periodof about 24 hours. After this time the reaction mixture was cooled toroom temperature, was filtered and stripped of acetone to yield a redviscous residue. The residue was dissolved in chloroform. The chloroformsolution was washed with water and dried over magnesium sulfate. Thedried solution was filtered and evaporated to yield the desired productS-[2-(6-methoxy-3 pyridylamino)-2-ketoethyl] O- ethylN-t-butylthiolophosphoramidate as a red viscous oil.

EXAMPLE 4 Preparation of S-[2-(6-methoxy-3-pyridylamino)2-ketoethyl]0,0-dimethyl thiolothionophosphate N-(G-methoxy 3-pyridyl)m-chloroacetamide (8.0 grams), potassium 0,0-dimethylthiolothionophosphate (9.41 grams) and acetone ml.) were charged into aglass reaction flask equipped with stirrer, thermometer and refluxcondenser. The reaction mixture was heated at reflux with stirring for aperiod of about 16 hours. After this time the reaction mixture wascooled, filtered and stripped of acetone to yield a residue. The residuewas extracted with chloroform and the chloroform solution washed withwater and dried over sodium sulfate. The dried solution was filtered andevaporated on a steam bath under vacuum to yield the desired product 8-[2-(6- methoxy-3-pyridylamino) 2-ketoethyl] 0,0-dimethylthiolothionophosphate as a red oil.

EXAMPLE 5 Prepartion of N-(4-methyl-2-pyridyl)-a-chloroacetamide Asolution of 2-amino-4-methylpyridine (10.8 grams) in ether ml.), andtriethylamine (10 grams) are placed in a reaction flask equipped withstirrer, thermometer and addition funnel. The reaction mixture is cooledto a temperature of about 0" C. and chloroacetyl chloride (11.3 grams)dissolved in ether (30 ml.) is slowly added thereto resulting in theformation of a precipitate. Stirring is continued for a period of about1 hour. After this time the reaction mixture is filtered to recover theprecipitate that has formed. The precipitate is washed with aqueouspotassium carbonate and with water. The washed precipitate is then driedto yield the desired product N-(4 methyl-2pyridyl) -a-chloroacetamide.

EXAMPLE 6 Preparation of O-[2-(4-methyl-2-pyridylamino)-2-ketoethyl]O-(3,4-dichlorophenyl) methylphosphonate N-(4-methyl-2 pyridyD-achloroacetamide (18.5 grams), potassium O-(3,4-dichlorophenyl)methylphosphonate (29.5 grams) and acetone (150 ml.) are charged into aglass reaction vessel equipped with a mechanical stirrer, thermometerand reflux condenser. The reaction mixture is stirred and heated atreflux for a period of about 18 hours. After this time the reactionmixture is cooled, filtered and stripped of acetone on a steam bath toyield a residue. The residue is extracted with chloroform and thechloroform solution is washed with water. The washed solution is driedover magnesium sulfate, is filtered and evaporated to yield the desiredproduct O-[2-(4-methyl-2-pyridylamino)-2-ketoethyl] O- (3,4-dichlorophenyl) methylphosphonate as the residue.

EXAMPLE 7 Preparation ofN-(2-chloro-6-ethoxy-3-pyridyl)-achloroacetamide A solution of2-chloro-3-amino-6-ethoxypyridine (17 grams) in ether (200 ml.), andtriethylamine (10 grams) are placed in a glass reaction flask equippedwith stirrer, thermometer and addition funnel. The mixture is cooled toabout to 10 C. and a solution of chloroacetyl chloride (11.3 grams) inether (40 ml.) is slowly added thereto over a period of about 30 minutesresulting in the formation of a precipitate. The precipitate isrecovered by filtration and is washed first with aqueous sodiumbicarbonate and then with water. The washed product is then dried toyield the desired product N-(2- cholro-6-ethoxy-3-pyridyl)-a-chloroacetamide.

EXAMPLE 8 Preparation of O-[2-(Z-chloro-6-ethoxy-3-pyridylamino)-2-ketoethy1] S,S-diisopropyl dithiolophosphate N-(2-chloro-6-ethoxy 3pyridyl)nut-chloroacetamide (25.1 grams), potassium S,S-diisopropyldithiolophosphate (25.2 grams) and acetone (250 ml.) are charged into aglass reaction flask equipped with stirrer, thermometer and refluxcondenser. The reaction mixture is then refluxed for a period of about36 hours. After this time the mixture is stripped of solvent and theresulting residue is dissolved in chloroform. The chloroform solution iswashed with water and is dried over magnesium sulfate. The driedsolution is filtered and evaporated to yield the desired productO-[2-(2-chloro-6-ethoxy-3- pyridylamino)2-ketoethyl] S,S-diisopropyldithiolophosphate.

EXAMPLE 9 Preparation ofN-(3-methoxy-5-bromo-2-pyridyl)-achloroacetamide A solution of2-amino-3-methoxy-S-bromopyridine (20.3 grams) in absolute ether (200ml.) is charged into a glass reaction vessel equipped with mechanicalstirrer and addition funnel. The solution is cooled to a temperature ofabout -C. and pyridine (20 ml.) is added thereto. A solution ofchloroacetyl chloride (11.3 grams) in ether (50 ml.) is then slowlyadded, with stirring, to the flask over a period of about 30 minutesresulting in the formation of a precipitate. The temperature of thereaction mixture is kept below about 10 C. during the addition of thechloroacetyl chloride and stirring is continued thereafter for a periodof about 1 hour to ensure the completion of the reaction. Theprecipitate which has formed is then recovered by filtration and iswashed first with aqueous potassium carbonate and then with wiater. Thewashed product is then dried in a vacuum desiccator to yield the desiredproduct N-(3- methoxy-5-bromo-2-pyridyl) -u-chloroacetamide.

EXAMPLE 10 Preparation of O-[2-(3-methoxy 5 bromo-2-pyridyl amino) 2ketoethyl] N,N-dimethyl methylphosphonamidate N-(3methoxy-S-bromo-Z-pyridyl) a chloroacetamide (28.0 grams), potassiumN,N-dimethyl methylphosphonamidate (16.1 grams) and acetone (200 ml.)are charged into a glass reaction vessel equipped with a mechanicalstirrer, thermometer and reflux condenser. The reaction mixture isheated at reflux for a period of about 18 hours. After this time themixture is stripped of acetone on the steam bath and the resultingresidue is dissolved in ether (2 00 ml.) and is washed with Water. TheWashed solution is dried over magnesium sulfate, is filtered andevaporated to yield the desired product 'O-[2- (3 -methoxy 5bromo-Z-pyridylamino)-2-ketoethyl] N,N-dimethyl methylphosphonamidate.

EXAMPLE 11 Preparation of-N-(4-nitro-6-ethoxy-2-pyridyl)-achloroacetamide A solution of2-amino-4-nitro-6-ethoxypyridine (29.4 grams) in absolute ether ml.),and pyridine (25 grams) are charged into a glass reaction vesselequipped with stirrer, thermometer and addition funnel. The mixture iscooled to a temperature of about 0 C. and chloroacetal chloride (11.3grams) dissolved in ether (50 ml.) is then slowly added thereto Withstirring over a period of about 20 minutes. Stirring and cooling arecontinued for an additional period of about 30 minutes. The resultingprecipitate is then recovered from the reaction medium by filtration, iswashed first with aqueous sodium carbonate and then with water, and isdried to yield the desired product N(4-nitro-6-ethoxy-2-pyridyl)a-chloroacetamide.

EXAMPLE 12 Preparation of S-[2-(4nitro-6-ethoxy-2-pyridylamino)-2-ketoethyl] diisopropylthiolophosphinate N-(4 nitro 6ethoxy-2-pyridyl)-a-chloroacetamide (37.1 grams) and potassiumdiisopropylthiolophosphinate (12.2 grams) and acetone (250 ml.) arecharged into a glass reaction vessel equipped with mechanical stirrer,thermometer and reflux condenser. The reaction mixture is heated atreflux for a period of about 36 hours. After this time the reactionmixture is stripped of solvent on a steam bath and the resulting residueis dissolved in ether (150 ml.) and is washed with water. The washedsolution is then dried over anhydrous magnesium sulfate, is filtered andevaporated to yield the desired product S- [2 (4nitro-6-ethoxy-2-pyridylamino)-2-ketoethy1]diisopropylthiolophosphinate.

EXAMPLE 13 Preparation of N-(2,6-dimethyl-3-pyridyl)-achloroacetamide Asolution of 2,6-dimethyl-3-aminopyridine (24.9 grams) in ether (200ml.), and pyridine (21 grams) are charged into a glass reaction vesselequipped with mechanical stirrer, thermometer and addition funnel. Thereaction mixture is cooled to a temperature below about 10 C. andchloroacetyl chloride'(11.3 grams) is slowly added over a period ofabout 15 minutes. Stirring and cooling is continued for an additionalperiod of about 1 hour to ensure the completion of the reaction. Theresulting precipitate is then recovered by filtration, is washed withaqueous potassium carbonate and with water, and is dried to yield thedesired product N-(2,6-dimethoxy- 3-pyridyl)-a-chloroacetamide.

EXAMPLE 14 Preparation of O-[2-(2,6 dimethyl 3 pyridylamino)-2-ketoethyl] O-methyl O-(4-chlorophenyl) phosphate N-(2,6 dimethyl 3pyridyl)-a-chloroacetamide (32.2 grams), potassium O-methylO-(4-chlorophenyl) phosphate (26 grams) and acetone (200 ml.) arecharged into a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. The reaction mixture is heated atreflux for a period of about 24 hours. After this time the mixture isstripped of solvent on a steam bath and the resulting residue isdissolved in ether. The ether solution is Washed with Water and is driedover magnesium sulfate. The dried solution is then evaporated undervacuum to yield the desired product O-[2 (2,6dimethyl-3-pyridylamino)-2-ketoethyl] methyl O-(4-chlorophenyl)phosphate.

Additional compounds within the scope of the present invention can beprepared in a manner similar to that detailed in the foregoing examples.In the following examples are given the essential ingredients requiredto prepare the indicated named compounds by the procedures heretoforedescribed.

EXAMPLE 2-amino 3,5 diiodopyridine+chloroacetyl chloride +potassiumdiphenylthionophosphinate:O-[2 (3,5-diiodo 2 pyridylamino)-2-ketoethyl]diphenylthionophosphinate.

EXAMPLE 16 4-amino 2,6 dichloropyridine+chloroacetyl chloride +potassium(2 chloro 4 nitrophenyl)(3,4-dibromophenyl)ph0sphinate=0 [2 (2,6dichlor0-4-pyridylamino)-2-ketoethyl] (2 chloro 4 nitrophenyl) (3,4-dibromophenyl) pho sphinate.

EXAMPLE 17 2 amino 3 ethoxy-6-nitropyridine+chloroacetylchloride-[potassium ethy1(2 methyl 4 nitrophenyl) phosphinate=O-[2 (3ethoxy 6 nitro-2-pyridylamino) 2 ketoethyl]ethyl(2-methyl-4-nitrophenyl) phosphinate.

EXAMPLE 18 3-amino 6 butoxypyridine+chloroacetal chloride +potassium (2methoxy 4 chlorophenyl)(4-isopropylphenyl)phosphinate=0 [2(6-butoxy-3-pyridylamino) 2 ketoethyl] (2-methoxy-4-chlorophenyl) (4-isopropylphenyl)phosphinate.

EXAMPLE 19 3-amino 4 n-butyl-6-methoxypyridine+chloroacetylchloride+potassium 0-(3 methylthiophenyl) t-butylphosphonate=0 [2(4-n-butyl 3 pyridylamino)-2- ketoethyl] O-(B-methylthiophenyl)t-butylp'hosphonate.

EXAMPLE 20 4-amino 3 bromopyridine+chloroacetyl chloride +potassium S (3allyl-S-ethylphenyl) 4-dimethylaminophenyldithiolophosphonate:S [2 (3bromo- 4-pyridylamino) 2 ketoethyl] S-(3-allyl-5-ethylphenyl)4-dimethylaminophenyldithiolophosphonate.

EXAMPLE 21 3-amino 5 allylpyridine+chlor0acetyl ch1oride+po tassiumO-(3-methylsulfonylphenyl) O-(4 methylthiophenyl)phosphate=0 [2(5-allyl-3-pyridylamino)-2- ketoethyl]O-(3 methylsulfonylphenyl)O-(4-methylthiophenyl) phosphate.

8 EXAMPLE 22 3-amino 5 bromo-2,4-dichloropyridine+ehloroacetylchloride+potassium S-(3 dimethylaminophenyl) O-(2,4- dichlorobenzyl)thiolophosphate=0 [2 (5 bromo- 2,4-dichloro-3-pyridylamino) 2ketoethyl]S-(3-dimethylaminophenyl) O (2,4 dichlorobenzyl) thiol0phosphate.

EXAMPLE 23 Z-amino-S-chloro 3 nitropyridine+chloroacetylchloride+potassium O pentenyl N,N diethylphosphoramidate=O-[2-(5-chloro3 nitro-2-pyridylamino)-2 ketoethyl] O-pentenylN,N-diethylphosphoramidate.

EXAMPLE 24 4-arnino 2,5 dinitropyridine+chloroacetyl chlo'ride-f-potassium S-(2-n-propoxy 4 bromophenyl) N- methyl-N-secbutylthiolothionophosphoramidate=O-[2- (2,5-dinitro-4-pyridylamino) 2ketoethyl] S(2-n-propoxy-4-bromophenyl)N-methyl-N-sec-butylthiolothionophosphoramidate.

EXAMPLE 25 2-amino-3,5-dibromo 4 ethylpyridine+chloroacetylchloride+potassium S- isopropyl S-(4-n-pentylsulfinylphenyl)tetrathiophosphate:S-[2-(3,5-dibromo-4-ethyl-2-pyridylamino)2-ketoethyl] S-isopropyl S-(4-n-penty1- sulfinylphenyl)tetrathiophosphate.

Additional compounds within the scope of the present invention that canbe prepared by the mtthods detailed in the foregoing examples but whichare not intended to limit this invention thereto are:

0- [2- (6-methylthio-3-pyridylamino -2-ketoethyl] S-tbutylallylthiolophosphonate S- [2- (4-chloro-5-allyl-3-pyridylamino-2-ketoethyl] O- (2,4-dichloro-6-pentenylphenyl) hexylthiolophosphonateS- [2- 6-isopropyl-4-ethoxy-2-pyridylamino -2-ketoethyl]S-(2,6-diethoxy-4-iodophenyl)4-di-n-propylaminophenyldithiolophosphonate 0- [2-(5-allyl-2-pyridylamino -2-ketoethyl] O- (3-diethylsulfinylphenyl)3-n-butoxy-5-allylphenethylthionophosphonate O- [2-(2-n-hexyl-S-chloro-S-pyridylamino -2-ketoethyl] For practical use asinsecticides or acaricides, the compounds of this invention aregenerally incorporated into insecticidal or acaricidal compositionswhich comprise an inert carrier and an insecticidally or acaricidallytoxic amount of such a compound. Such insecticidal or acaricidalcompositions, which can also be called formulations, enable the activecompound to be applied conveniently to the site of the insect or acaridinfestation in any desired quantity. These compositions can be solidssuch as dusts, granules or wettable powders; or they can be liquids suchas solutions, aerosols or emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the tales, clays, silicas,'pyrophyllite, and the like. Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, ontoand into granulated carriers such as the attapulgites or thevermiculites, usually of a particle size range of from about 0.3 to 1.5mm. Wettable powders, which can be dispersed in water and/or oil to anydesired concentration of the'active compound, can be prepared byincorporating wetting agents into concentrated dust compositions.

In some cases the active compounds are sufficiently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofinsecticides or acaricides can be dispersed under superatmosphericpressure as aerosols. However, preferred liquid insecticidal oracaricidal compositions are emulsifiable concentrates, which comprise anactive compound according to this invention and as the inert carrier, asolvent and an emulsifier. Such'emulsifiable concentrates can beextended with water and/or oil to any desired concentration of activecompound for application as sprays to the site of the insect or acaridinfestation. The emulsifiers most commonly used in these concentratesare nonionic or mixtures of nonionic with anionic surface-active agents.

A typical insecticidal or acaricidal composition according to thisinvention is illustrated by the following example, in which thequantities are in parts by weight.

EXAMPLE 26 PreparatiQ i ofa dust Product of Example 2 1O Powdered talc'90 The above ingredients are mixed in a mechanical grinder-blender andare ground until a homogeneous, freeflowing'dust of'the desired particlesize is obtained. This dust is'suitable for direct application'to thesite of the insector acarid infestation.

--The:compounds of this invention can be applied as insecticidesor'acaricides in any manner recognized by the '-'art.- One method fordestroying insects or acarids comprises applying to the locus of theinsect or acarid infestation, an insecticidal or acaricidal compositioncomprising .an inert carrier and, as an essential active ingredient, ina quantity which is toxic to said insects or acarids,;a compound of thepresent invention. The concentration of the new compounds of thisinvention in the insecticidal or acaricidal compositions will varygreatly with the type of formulation and the purpose for which it isdesigned, but generally the insecticidal or acaricidal compositions willcomprisefrom about 0.05 to about 95 percent by weight of the activecompounds of this invention. In a preferred embodiment of thisinvention, the insecticidal or acaricidal compositions will comprisefrom about 5 to 75 percent by weight of the active compound. Thecompositions can also comprise such additional sub stances as otherpesticides, stabilizers, Spreaders, deactivators, adhesives, stickers,fertilizers, activators, synergists, and the like.

The compounds of the present invention are also useful when combinedwith other insecticides or acaricides in the compositions heretoforedescribed. These other insecticides or acaricides can comprise fromabout 5% to about 95% of the active ingredients in the compositions. Useof the combinations of these other insecticides or acaricides with thecompounds of the present invention provide insecticidal and/ oracaricidal compositions which are more effective in controlling insectsor acarids and often provide results unattainable with separatecompositions of the individual compounds. The other insecticides oracaricides with which the compounds of this invention can be used in theinsecticidal or acaricidal compositions to control insects or acaridsinclude halogenated compounds such as DDT, methoxychlor, TDE, lindane,chlordane, isobenzan, aldrin, dieldrin, heptachlor, endrin, mirex,endosulfon, dicofol, and the like; organic phosphorus compounds such asTEPP, schradan, ethion, parathion, methyl parathion, EPN, demeton,carbophenothion, phorate, zinophos, diazinon, malathion, mevinphos,dimethoate, DBD, ronnel, oxydemeton-methyl, dicapthon, chlorothion,phosphamidon, naled, fenthion, trichlorofon, DDVP, and the like; organicnitrogen compounds such as dinitro-o-cresol, dinitrocyclohexylphenol,DNB, DNP, zinapacril, azobenzene, and the like; organic carbamatecompounds such as carbaryl, ortho 5353, and the like; organic sulfurcompounds such as phenothiazine, phenoxathin, lauryl thiocyanate,[bis(2-thiocyanoethyl)ether], isobornyl thiocyanoacetate, and the like;as Well as such substances usually referred to as fumigants, as hydrogencyanide, carbon tetrachloride, calcium cyanide, carbon disulfide,ethylene dichloride, propylene dichloride, ethylene dibromide, ethyleneoxide, methyl bromide, paradichlorobenzene, and the like.

The compounds of the present invention can also be combined withfungicidal and nematocidal chemical compounds to form pesticidalcompositions useful for the control of fungi and in some cases soilnematodes as well as insects or acarids. Typical examples of suchfungicidal chemical compounds are ferbam, nabam, zineb, ziram, thiram,chloranil, dichlone, glyodin, cycloheximide, dino cap, maneb, captan,dodine, PCNB, p dimethylaminobenzenediazo sodium sulfonate, and thelike; While examples of nematociadal compounds are chloropicrin, 0,0-diethyl O-(2,4 dichlorophenyl)phosphorothioate, tetrachlorothiophene,dazomet, dibromochloropropane, and the like.

The new compounds of this invention can be used in many ways for thecontrol of insects or acarids. Insecticides or acaricides which are tobe used as stomach poisons or protective materials can be applied to thesurface on which the insects or acarids feed or travel. Insecticides oracaricides which are to be used as contact poisons or eradicants can beapplied directly to the body of the insect or acarid, as a residualtreatment to the surface on which the insect or acarid may walk orcrawl, or as a fumigant treatment of the air which the insect or acaridbreathes. In some cases, the compounds applied to the soil or plantsurfaces are taken up by the plant, and the insects or acarids arepoisoned systemically.

The above methods of using insecticides are based on the fact thatalmost all the injury done by insects is a direct or indirect result oftheir attempts to secure food. Indeed, the large number of destructiveinsects can be classified broadly on the basis of their feeding habits.Among the insects which can be effectively controlled by the compoundsof the present invention are the chewing insects, such as the Mexicanbean beetle and the southern armyworm; the piercing-sucking insects,such as the pea aphid, the cereal leaf beetle, the housefly, the grapeleafhopper, the chinch bug, the lygus bug, the oyster shell scale, theCalifornia red scale, the Florida red scale, the soft scale andmosquitoes; the internal feeders, including borers, such as the Europeancorn borer, the peach twig borer and the corn earworm, worms or weevils,such as the codling moth, the alfalfa weevil, the cotton boll weevil,the pink boil worm, the plum curculio, the red banded leaf roller, themelonworm, the cabbage looper and the apple maggot, leaf miners, such asthe apple leaf miner, the birch leaf miner and the beet leaf miner, andgall insects, such as the wheat joint worm and the grape phylloxera.Insects which attack below the surface of the ground are classified assubterranean insects and include such destructive pests as the woolyapple aphid, the Japanese beetle, the onion maggot and the cornrootworm.

Mites and ticks are not true insects. Many economically importantspecies of mites and ticks can be controlled by the compounds of thepresent invention, such as the red spider mite, the two-spotted mite,the strawberry spider mite, the citrus rust mite, the cattle tick, thepoultry mite, the citrus red mite and the European red mite. Chemicalsuseful for the control of mites are often called miticides, while thoseuseful for the control of both mites and ticks are known specifically asacaricides.

The quantity of active compound of this invention to be used for insector acarid control will depend on a variety of factors, such as thespecific insect involved, intensity of the infestation, weather, type ofenvironment, type of formulation, and the like. For example, theapplication of only one or two ounces of active chemical per acre may beadequate for control of a light infestation of an insect or acarid underconditions unfavorable for its feeding, while a pound or more of activecompound per acre may be required for the control of a heavy infestationof insects or acarids under conditions favorable to their development.

The insecticidal utility of the compounds of this invention wasdemonstrated by experiments carried out for the control of a variety ofinsects.

In one experiment carried out for the control of the housefly,designated as the housefly topical test, each of fifty flies wascontacted with a test compound by applying 1 ,ul. of test formulation,containing the indicated concentrations of active compound, to thedorsum of its thorax. The flies were then placed in a wire mesh cagewhere they were supplied with sugar syrup. At the end of a 24 hourperiod the mortality of the flies was observed and rated in comparisonto a control. The results of this experiment are shown in Table I.

TABLE I Concentration of test compound Percent Test compound in p.p.m.mortality Product of- Example 2 a, 500 100 Example 3 3, 500 92 Example 43, 500 94 The insecticidal activity of the compounds of this inventionwas further illustrated in experiments carried out for the control ofthe pea aphid (Acyrthosiphonv pisum) by contact. In these experimentsten day old Laxton pea plants contained in small plastic pots were eachinfested with ten adult pea aphids. The plants and pea aphids were thensprayed with the test compound formulated as an aqueous emulsion of anacetone solution at various concentrations. The infested plants werethen placed in a holding chamber maintained at a constant temperaturefor a period of 48 hours. After this time the mortality of the aphidswas determined and rated on a percent basis in comparison to a control.The results of this experiment are shown in Table II.

The systemic activity of the compound of this invention was demonstratedin experiments for the systemic control of pea aphids. In theseexperiments 5 day old Laxton pea plants which had previously beenWatered with 30 ml. of water containing the test compound at theindicated concentration, were infested with ten newly TAB LE IIIConcentration of test compound Percent Test compound in p.p.m. mortalityProduct of- Example 2 100 Example 3 100 100 The acaricidal activity ofthe compounds of the present invention was demonstrated in experimentscarried out for the control of the two-spotted spider mite (Tetranychusurticae).

In one experiment wherein the activity of the compounds of the presentinvention as contact poisons was determined, the test compounds wereformulated at the indicated dosages, as aqueous emulsions of acetoneSolutions and were sprayed onto Henderson bush lima bean plants, eachinfested with about 100 adult two-spotted spider mites. The treatedplants were then placed into a holding room and were supplied with theirdaily requirement of water and light. After a period of 5 days themortality of the mites is determined and is rated on a percent basis incomparison to untreated controls. The results of this experiment areshown in Table IV.

In another experiment the systemic activity of the compounds of thisinvention, for the control of the twospotted spider mite wasdemonstrated. In this experiment 5 day old Henderson bush lima beanplants were each watered with 30 ml. of a formulation containing thetest compound at the indicated concentration. After a period of 48 hoursthe plants were infested with twospotted spider mites and were placedinto a holding room and supplied with water and light as required. Aftera period of 5 days the mortality of the mites is determined and rated ona percent basis in comparison to untreated controls. The results of thisexperiment are shown in Table V.

1. An insecticidal composition comprising an inert carrier and aninsecticidally effective amount of a compound of the formula wherein -Ris selected from the group consisting of lower alkyl, lower alkenyl andwherein A is selected from the group consisting of lower alkyl, loweralkenyl, lower alkoxy, lower alkylthio, halogen, nitro, di(lower alkyl)amino, lower alkylsulfoxide, and lower alkyl sulfone, q is an integerfrom 0 to 5, and p is an integer from 0 to 3; X X and X areindependently selected from the group consisting of oxygen and sulfur; mis an integer from O to 1; Y is selected from the group consisting oflower alkylamino and di(lower alkyl) amino; R is lower alkyl; Z isselected from the group consisting of lower alkyl, lower alkenyl, loweralkoxy, lower alkylthio, halogen and nitro, and n is an integer from 0to 4.

2. A method of controlling insects which comprises applying aninsecticidally effective amount of the composition of claim 1 to saidinsects.

3. The method of claim 2 wherein the compound isS-[2-(6-methoxy-3-pyridylamino)-2 ketoethyl] O-ethylN-isopropylthiolophosphoramidate.

4. The method of claim 2 wherein the compound isS-[2-(6-methoxy-3-pyridylamino)-2 ketoethyl] O-ethylN-t-butylthiolophosphoramidate.

References Cited UNITED STATES PATENTS 2/1968 Lorenz et a1. 260294.8 K1/1972 Richter et a1. 260294.8 K

5 /1 i UNITED sir/mas PATENT OFFICE m 1 w 1 r I.

CERTIFICATIL bl? CORREC HON 1. emmneli,r1214..-

Inventor) Sidnev B. Richter and Lennard .T. qi-agfh It is certified thaterror appears in the above-identifiedpatent and that said Letters Patentare hereby corrected as shown below:

Tr 1 column 3, lines 11 to 16 the portion of formula :III appearingshould read as follows:

In column 4, line 4 for "N- (16-methoxy-3-pyridyl) -".'l-chloroacet readN -(6-methoxy-3-pyridyl)-d-ch-loroacet- In column 6; line 36 for"acetal" read acetyl In column 7, line 50 for "chloroacetal" read,chloroacetyl In column 10, line 17 for "zinapacril'l read binapacrilSigned and sealed this 24th day of September 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR. 0. MARSHALL DANN Commissioner of Patents AttestingOfficer

